WO2014000849A2 - Method for coating a substrate with a spray material and functional layer achievable with this method - Google Patents

Method for coating a substrate with a spray material and functional layer achievable with this method Download PDF

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Publication number
WO2014000849A2
WO2014000849A2 PCT/EP2013/001574 EP2013001574W WO2014000849A2 WO 2014000849 A2 WO2014000849 A2 WO 2014000849A2 EP 2013001574 W EP2013001574 W EP 2013001574W WO 2014000849 A2 WO2014000849 A2 WO 2014000849A2
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WO
WIPO (PCT)
Prior art keywords
weight
functional layer
crä
wire
substrate
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Application number
PCT/EP2013/001574
Other languages
German (de)
French (fr)
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WO2014000849A3 (en
Inventor
Eyuep Akin ÖZDENIZ
Rainer Joos
Wolfgang Hansen
Michael Walker
Ümit AKAY
Original Assignee
Daimler Ag
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Application filed by Daimler Ag filed Critical Daimler Ag
Priority to EP13726117.8A priority Critical patent/EP2867383A2/en
Priority to CN201380034644.6A priority patent/CN104603318B/en
Priority to JP2015517626A priority patent/JP6053230B2/en
Priority to US14/405,867 priority patent/US9988701B2/en
Publication of WO2014000849A2 publication Critical patent/WO2014000849A2/en
Publication of WO2014000849A3 publication Critical patent/WO2014000849A3/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0227—Rods, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying

Definitions

  • the invention relates to a method for coating a substrate, in which a wire-shaped spray material is melted in an arc and deposited as a layer on the substrate.
  • the invention also relates to a corrosion-resistant functional layer which can be produced with sufficiently high hardness and tribologically favorable properties.
  • engine components such as cylinder bores or their walls are provided with a tread layer or it liners are inserted into the cylinder bores, which with a
  • Tread layer are provided.
  • the application of such tread layers mostly takes place by means of thermal spraying, for example electric arc wire spraying.
  • Arc wire spraying is an arc generated by applying a voltage between two wire-shaped spray materials.
  • the wire tips melt and are conveyed, for example, by means of a nebulizer gas to the surface to be coated, for example, the cylinder wall, where they accumulate.
  • a cylinder liner for Ver is ⁇ brennungskraftmaschinen known which comprises a base body with a wear-resistant coating on the running surface on ⁇ , tensit Bear based on a hard iron alloy having a Mar-, wherein the wear-resistant layer in the electric arc wire spray process is coatable, and the alloy the coating has inter alia a carbon content of 0.05 to 3 wt .-% and a chromium content of 9 to 13 wt .-%.
  • a method for producing a coating by means of arc wire spraying is known, in which a chromium-containing iron alloy is supplied with 0.5 to 8% by weight of boron carbide. The supply of boron carbide
  • the boron carbide content acts embrittling, i. leads to increased cracking of layers produced thereby, and such layers have a strong abrasive action against tribological partners.
  • Diesel engines can meet advantageous dimensions. It is therefore an object of the invention to specify an improved method for arc wire spraying and a functional layer that can be produced therewith.
  • Target variables are, in addition to good spray behavior, specific properties of the functional layer, in particular good machinability.
  • the layer properties also include sufficient corrosion resistance, as well as sufficient hardness, which should be in the range of 400 to 650 HV 0.1. Layers with these properties should be able to be produced without additional delivery equipment and contain no boron or boron carbide.
  • Iron base comprising the following alloying components specified in the parameters nickel equivalent (Ni ⁇ ) and
  • the Schwarzer diagram is a common representation of parameters that provide information about structural fractions in the weld metal of alloyed steels and is here as FIG. 1
  • the desired corrosion resistance of the functional layer to be produced requires at least a chromium equivalent of 10.
  • the Cr content in the spray wire must be selected so that the evaporation during the process is done. Investigations have shown that the definition of the alloy composition of the spray wire must consider evaporation of up to 0.5% by weight of chromium in the wire. This results in a minimal for the spray wire
  • the functional layer to be produced should have sufficient hardness for the loads of diesel engines, i. at least on the order of 350 to 400 HV 0.1, preferably above.
  • it should have sufficient tribological properties, in particular have the lowest possible adhesive tendency towards the tribological partner, i. in case of a
  • Raceway coating should not tend to weld locally with the piston. Therefore, and to set the required minimum hardness, the functional layer should essentially have a martensitic structure and
  • Austenitic shares should be avoided as much as possible. Ferritic shares should also be avoided as much as possible, but can be tolerated to a small extent. In addition, a martensitic microstructure is advantageous for the functional layer for three further reasons:
  • the thermal expansion coefficient of martensite is significantly lower than that of austenite. As a result, the risk of austenite is reduced, that the functional layer contracts on cooling more than the substrate and thereby dissolves.
  • the martensitic transformation produces residual compressive stresses which improve the bond to the substrate and also counteract the formation of cracks in the coating.
  • the thermal conductivity in the martensitic state is the thermal conductivity of the martensitic state.
  • the functional layer is deposited by means of arc wire spraying (LDS).
  • LDS arc wire spraying
  • two wire-shaped spray materials are fed to a coating head.
  • wire-shaped spray materials an arc is ignited.
  • the wire-shaped spray material melts and is selectively applied by means of a carrier gas to the substrate to be coated, where it cools, solidifies and the
  • the wire-shaped spray material essentially comprises an iron-chromium alloy.
  • the spray material is formed at least with carbon as a micro-alloy in such a way that predominantly martensite is formed during the cooling of the spray material, almost no austenite and only small amounts of ferrite.
  • the chromium equivalent results from a chromium content of 12.3 wt .-% and a silicon content of 0.38 wt .-%.
  • the nickel equivalent results from a nickel Proportion of 0.3 wt .-%, a carbon content of 0.18 wt .-% and a manganese content of 0.4 wt .-%.
  • Functional layer are Cu, Al and V, each with just under 0.1 wt .-% and in minor lanes P, W, Co, Mo and S.
  • the main component of the alloy is iron.
  • the quantities are in percent by weight in each case based on a total weight, unless otherwise specified.
  • the functional layer according to the invention is characterized in particular by a high hardness and resistance to diesel fuel with a high sulfur content of 500 to 1000 ppm, while functional layers according to the prior art
  • the coating of the substrate takes place in which the wire-shaped spray material in an arc
  • Spray material in the arc is preferably carried out at a melting capacity of at least 9000 W, in particular with a current of at least 250 A and / or a voltage of at least 36 V.
  • a melting capacity of at least 9000 W in particular with a current of at least 250 A and / or a voltage of at least 36 V.
  • the wire-shaped spray material 4 is advantageously conveyed at a maximum speed of 12 m / s and the jet of molten particles with a

Abstract

The invention relates to a method for coating a substrate in which a wire-shaped spray material is melted in an arc and is deposited as a functional layer on the substrate. The invention also relates to a functional layer which can be produced on the substrate by this method. The functional layer has a high hardness value and good corrosion resistance on exposure to diesel fuel with a high sulphur content.

Description

Verfahren zum Beschichten eines Substrats mit einem Spritzwerkstoff und damit erzeugbare .Funktionsschicht  Process for coating a substrate with a spray material and the functional layer that can be produced therewith
Die Erfindung betrifft ein Verfahren zum Beschichten eines Substrats, bei dem ein drahtförmiger Spritzwerkstoff in einem Lichtbogen aufgeschmolzen und als Schicht auf dem Substrat abgeschieden wird. Die Erfindung betrifft außerdem eine damit erzeugbare korrosionsbeständige Funktionsschicht mit ausreichend hoher Härte und tribologisch günstigen Eigenschaften. The invention relates to a method for coating a substrate, in which a wire-shaped spray material is melted in an arc and deposited as a layer on the substrate. The invention also relates to a corrosion-resistant functional layer which can be produced with sufficiently high hardness and tribologically favorable properties.
Bei der Herstellung von Verbrennungsmotoren wird aus Gründen der Energieeffizienz und der Emissionsreduzierung eine möglichst geringe Reibung und eine hohe Abrieb- und In the manufacture of internal combustion engines for reasons of energy efficiency and emission reduction as low as possible friction and high abrasion and
Verschleißfestigkeit angestrebt. Hierzu werden Motorbauteile, wie zum Beispiel Zylinderbohrungen bzw. deren Wandungen mit einer Laufflächenschicht versehen oder es werden Laufbuchsen in die Zylinderbohrungen eingesetzt, welche mit einer Wear resistance sought. For this purpose, engine components, such as cylinder bores or their walls are provided with a tread layer or it liners are inserted into the cylinder bores, which with a
Laufflächenschicht versehen werden. Das Aufbringen solcher Laufflächenschichten erfolgt zumeist mittels thermischen Spritzens, beispielsweise Lichtbogendrahtspritzen. Beim Tread layer are provided. The application of such tread layers mostly takes place by means of thermal spraying, for example electric arc wire spraying. At the
Lichtbogendrahtspritzen wird zwischen zwei drahtförmigen Spritzwerkstoffen ein Lichtbogen durch Anlegen einer Spannung erzeugt. Dabei schmelzen die Drahtspitzen ab und werden beispielsweise mittels eines Zerstäubergases auf die zu beschichtende Oberfläche, beispielsweise die Zylinderwand befördert, wo sie sich anlagern. Arc wire spraying is an arc generated by applying a voltage between two wire-shaped spray materials. In this case, the wire tips melt and are conveyed, for example, by means of a nebulizer gas to the surface to be coated, for example, the cylinder wall, where they accumulate.
Aus der DE 10308563 B3 ist eine Zylinderlaufbuchse für Ver¬ brennungskraftmaschinen bekannt, welche einen Grundkörper mit einer Verschleißschutzbeschichtung auf der Lauffläche auf¬ weist, auf Basis einer harten Eisenlegierung mit einer Mar- tensitbildung, wobei die Verschleißschutzschicht im Licht- bogendrahtspritzverfahren auftragbar ist und die Legierung der Beschichtung u. a. einen Kohlenstoffgehalt von 0,05 bis 3 Gew.-% und einen Chromgehalt von 9 bis 13 Gew.-% aufweist. Aus der DE 102007010698 AI ist ein Verfahren zur Herstellung einer Beschichtung mittels Lichtbogendrahtspritzen bekannt, bei dem eine Chrom-haltige Eisenlegierung mit 0,5 bis 8 Gew.- % Borcarbid zugeführt wird. Die Zufuhr von Borcarbid From DE 10308563 B3 a cylinder liner for Ver is ¬ brennungskraftmaschinen known which comprises a base body with a wear-resistant coating on the running surface on ¬, tensitbildung based on a hard iron alloy having a Mar-, wherein the wear-resistant layer in the electric arc wire spray process is coatable, and the alloy the coating has inter alia a carbon content of 0.05 to 3 wt .-% and a chromium content of 9 to 13 wt .-%. From DE 102007010698 Al a method for producing a coating by means of arc wire spraying is known, in which a chromium-containing iron alloy is supplied with 0.5 to 8% by weight of boron carbide. The supply of boron carbide
ermöglicht die Bildung von Eisenborid und führt so zu einer Erhöhung der Schichthärte. Allerdings erhöht dies die allows the formation of iron boride and thus leads to an increase in the layer hardness. However, this increases the
Verfahrenskosten und verschlechtert die Zerspanbarkeit . Process costs and deteriorates the machinability.
Es ist bekannt, dass kommerzielle Schichtsysteme auf der Basis von niedriglegierten Eisen-Kohlenstofflegierungen in Analogie zu Gusseisen-Oberflächen, zu Korrosion neigen. Dem kann durch Einbringen von Chrom begegnet werden. Andererseits erzielen bislang untersuchte Chrom-haltige Schichten die erforderliche Härte nur durch z.B. zusätzliches Einbringen von Hartstoffteilchen wie z.B. Borkarbid. Dies wiederum bedarf eine von der Drahtf rderung unabhängige aufwändige Zuführung von Pulver mittels Pulverförderung oder die It is known that commercial coating systems based on low-alloyed iron-carbon alloys, in analogy to cast iron surfaces, tend to corrode. This can be counteracted by introducing chromium. On the other hand, chromium-containing layers investigated so far achieve the required hardness only by e.g. additional introduction of hard material particles such as e.g. Boron carbide. This, in turn, requires an expensive feeding of powder by means of powder conveyance, or one which is independent of the wire feed
Verwendung von kostenintensiven Fülldrähten. Darüber hinaus wirkt der Borkarbid-Anteil versprödend, d.h. führt zur vermehrten Rissbildung damit erzeugter Schichten, und solche Schichten haben gegenüber tribologischen Partnern eine stark abrasive Wirkung. Use of costly cored wires. In addition, the boron carbide content acts embrittling, i. leads to increased cracking of layers produced thereby, and such layers have a strong abrasive action against tribological partners.
Zur Vermeidung dieser Nachteile wurde in der DE 102010021300 AI auf die Einbringung von Bor verzichtet und stattdessen die Härte der aufgebrachten Funktionsschicht durch einen hohen Kohlenstoffanteil von mindestens 0,7 Gew.-% in der In order to avoid these disadvantages, the incorporation of boron was dispensed with in DE 102010021300 A1 and instead the hardness of the applied functional layer was replaced by a high carbon content of at least 0.7% by weight in the
zugeführten Eisenlegierung eingestellt. supplied iron alloy set.
Es hat sich jedoch gezeigt, dass die damit erzeugten However, it has been shown that the generated
Funktionsschichten zumindest für die Laufbahnbeschichtung von Dieselmotoren keine ausreichende Härte erreichen und auch weitere tribologische Anforderungen nicht in einem für Functional layers, at least for the raceway coating of diesel engines not reach sufficient hardness and also no other tribological requirements in a for
Dieselmotoren vorteilhaftem Maße erfüllen können. Es ist daher eine Aufgabe der Erfindung, ein verbessertes Verfahren zum Lichtbogendrahtspritzen sowie eine damit herstellbare Funktionsschicht anzugeben. Zielgrößen sind dabei neben gutem Spritzverhalten, gezielte Eigenschaften de Funktionsschicht, insbesondere gute Bearbeitbarkeit . Die Schichteigenschaften beinhalten außerdem eine ausreichende Korrosionsbeständigkeit, sowie hinreichende Härte, die im Bereich 400 bis 650 HV 0,1 liegen sollte. Schichten mit diesen Eigenschaften sollen ohne zusätzliche Förderungseinrichtungen hergestellt werden können und kein Bor oder Borkarbid enthalten. Diesel engines can meet advantageous dimensions. It is therefore an object of the invention to specify an improved method for arc wire spraying and a functional layer that can be produced therewith. Target variables are, in addition to good spray behavior, specific properties of the functional layer, in particular good machinability. The layer properties also include sufficient corrosion resistance, as well as sufficient hardness, which should be in the range of 400 to 650 HV 0.1. Layers with these properties should be able to be produced without additional delivery equipment and contain no boron or boron carbide.
Die Aufgabe wird erfindungsgemäß gelöst durch eine Funktions schicht mit den Merkmalen des Anspruchs 1 sowie durch ein Verfahren zum Beschichten eines Substrats mit einem draht- förmigen Spritzwerkstoff mit den Merkmalen des Anspruchs 3. Vorteilhafte Weiterbildungen sind Gegenstand der The object is achieved by a functional layer with the features of claim 1 and by a method for coating a substrate with a wire-shaped spray material with the features of claim 3. Advantageous further developments are the subject of
Unteransprüche. Dependent claims.
Ein erfindungsgemäßes Verfahren zeichnet sich durch die Verwendung eines drahtförmigen Spritzwerkstoffes auf An inventive method is characterized by the use of a wire-shaped spray material
Eisenbasis aus, aufweisend folgende Legierungsbestandteile angegeben in den Kenngrößen Nickeläquivalent (NiÄ) und Iron base, comprising the following alloying components specified in the parameters nickel equivalent (NiÄ) and
Chromäquivalent (CrÄ) des Schäffler-Diagramms : Chromium equivalent (CrÄ) of the Schäffler diagram:
- CrÄ > 10,5 und  - CrÄ> 10.5 and
- NiÄ > CrÄ - 8 und  - NiÄ> CrÄ - 8 and
- NiÄ < 21 - 0,8*CrÄ  - NiA <21 - 0.8 * CrÄ
jeweils bezogen auf ein Gesamtgewicht. each based on a total weight.
Das Schäffler-Diagramm ist eine geläufige Darstellung von Kenngrößen, die Aufschluss über Gefügeanteile im Schweißgut von legierten Stählen geben und ist hier als Figur 1 The Schäffler diagram is a common representation of parameters that provide information about structural fractions in the weld metal of alloyed steels and is here as FIG. 1
wiedergegeben. Dabei werden die Austenit bildenden bzw. dies fördernden Legierungsbestandteile Nickel, Kohlenstoff und Mangan zu sogenannten Nickeläquivalenten (= NiÄ = Ni-Anteil [Gew.-%] + 30*C-Anteil [Gew.-%] +0 , 5*Mn-Anteil [Gew.-%]) und die Ferrit bildenden bzw. diese fördernden Legierungsbestandteile Chrom, Molybdän, Silizium, Niob und Titan zu sogenannten Chromäquivalenten (= CrÄ = Cr-Anteil [Gew.-%] + Mo- Anteil [Gew.-%] + 1, 5*Si-Anteil [Gew.-%] + 0 , 5*Nb-Anteil played. Here, the austenite-forming or promoting alloying components nickel, carbon and manganese to so-called nickel equivalents (= NiÄ = Ni content [wt .-%] + 30 * C content [wt .-%] +0, 5 * Mn Proportion [wt .-%]) and the ferrite-forming or promoting alloying components chromium, molybdenum, silicon, niobium and titanium to so-called chromium equivalents (= CrÄ = Cr fraction [wt .-%] + Mo fraction [wt .-%] + 1, 5 * Si Proportion [% by weight] + 0.5 * Nb content
[Gew.-%] + 2*Ti-Anteil [Gew.-%]) zusammengefasst und die sich abhängig von der Legierungszusammensetzung ausbildenden  [% By weight] + 2 * Ti content [% by weight]) and which are formed depending on the alloy composition
Gefügeanteile an Martensit, Austenit und Ferrit in deren Abhängigkeit dargestellt. Particles of martensite, austenite and ferrite are shown in their dependency.
Die angestrebte Korrosionsbeständigkeit der herzustellenden Funktionsschicht erfordert mindestens ein Chromäquivalent von 10. Dafür muss der Cr-Anteil im Spritzdraht so gewählt werden, dass dem Verdampfen während des Prozesses genüge getan wird. Untersuchungen haben gezeigt, dass die Definition der Legierungszusammensetzung des Spritzdrahtes ein Abdampfen von bis zur 0,5 Gew.-% Chrom im Draht berücksichtigen muss. Dadurch ergibt sich für den Spritzdraht ein minimales The desired corrosion resistance of the functional layer to be produced requires at least a chromium equivalent of 10. For this, the Cr content in the spray wire must be selected so that the evaporation during the process is done. Investigations have shown that the definition of the alloy composition of the spray wire must consider evaporation of up to 0.5% by weight of chromium in the wire. This results in a minimal for the spray wire
Chromäquivalent von 10,5. Chromium equivalent of 10.5.
Die herzustellende Funktionsschicht soll einerseits eine ausreichende Härte für die Belastungen von Dieselmotoren aufweisen, d.h. mindestens in der Größenordnung von 350 bis 400 HV 0,1 aufweisen, vorzugsweise darüber. Andererseits soll sie ausreichende tribologische Eigenschaften aufweisen, insbesondere möglichst geringe adhäsive Neigung gegenüber dem tribologischen Partner haben, d.h. im Falle einer On the one hand, the functional layer to be produced should have sufficient hardness for the loads of diesel engines, i. at least on the order of 350 to 400 HV 0.1, preferably above. On the other hand, it should have sufficient tribological properties, in particular have the lowest possible adhesive tendency towards the tribological partner, i. in case of a
Laufbahnbeschichtung soll diese nicht dazu neigen, mit dem Kolben lokal zu verschweißen. Deshalb und zur Einstellung der erforderlichen Mindesthärte soll die Funktionsschicht im Wesentlichen ein martensitisches Gefüge aufweisen und Raceway coating should not tend to weld locally with the piston. Therefore, and to set the required minimum hardness, the functional layer should essentially have a martensitic structure and
austenitische Anteile sollten weitestgehend vermieden werden. Ferritische Anteile sollen ebenfalls möglichst vermieden werden, können aber in geringem Umfang toleriert werden. Darüber hinaus ist eine martensitische Gefügestruktur aus drei weiteren Gründen vorteilhaft für die Funktionsschicht: Austenitic shares should be avoided as much as possible. Ferritic shares should also be avoided as much as possible, but can be tolerated to a small extent. In addition, a martensitic microstructure is advantageous for the functional layer for three further reasons:
Der thermische Ausdehnungskoeffizient von Martensit ist deutlich niedriger als derjenige von Austenit. Dadurch wird die bei Austenit bestehende Gefahr verringert, dass sich die Funktionsschicht beim Abkühlen stärker als das Substrat zusammenzieht und dadurch ablöst. The thermal expansion coefficient of martensite is significantly lower than that of austenite. As a result, the risk of austenite is reduced, that the functional layer contracts on cooling more than the substrate and thereby dissolves.
In der Funktionsschicht entstehen durch die martensitische Umwandlung Druckeigenspannungen, welche die Anbindung zum Substrat verbessern und zudem der Bildung von Rissen in der Beschichtung entgegenwirken. In the functional layer, the martensitic transformation produces residual compressive stresses which improve the bond to the substrate and also counteract the formation of cracks in the coating.
Die Wärmeleitfähigkeit im martensitischen Zustand ist The thermal conductivity in the martensitic state is
gegenüber dem austenitischen Gefüge deutlich erhöht. Dies führt zu einer verbesserten Wärmeabfuhr aus der Zylinderwand in den Wassermantel, was sich wiederum günstig auswirkt auf die thermische Bauteilbelastung und das tribologische significantly increased compared to the austenitic structure. This leads to improved heat removal from the cylinder wall in the water jacket, which in turn has a favorable effect on the thermal component load and the tribological
Verhalten der Laufbahn gegenüber Kolben/Kolbenring. Behavior of the raceway relative to piston / piston ring.
Versuche zeigen, dass diese Eigenschaften gegeben sind, wenn folgende Rahmenbedingungen für die Legierungsbestandteile der Funktionsschicht angegeben in den Kenngrößen Nickeläquivalent und Chromäquivalent des Schäffler-Diagramms erfüllt sind: 19 - 0,8CrÄ > NiÄ > CrÄ - 9. Experiments show that these properties are given if the following conditions for the alloy constituents of the functional layer specified in the parameters nickel equivalent and chromium equivalent of the Schäffler diagram are met: 19 - 0.8CrÄ> NiÄ> CrÄ - 9.
Auch hierbei muss das Abdampfen von Legierungsbestandteilen des Spritzdrahtes während des thermischen Beschichtens berücksichtigt werden. Untersuchungen haben gezeigt, dass ein Abdampfen von bis zur 0,25 Gew.-% C im Spritzdraht vorkommen kann. Ähnliches gilt für weitere Bestandteile des Spritz¬ drahtes. Dadurch ergeben sich für den verfahrensgemäß zu verwendenden Spritzdraht folgende Rahmenbedingungen: 21 - 0,8*CrÄ > NiÄ > CrÄ - 8. Again, the evaporation of alloy components of the spray wire during thermal coating must be considered. Investigations have shown that evaporation of up to 0.25 wt .-% C can occur in the spray wire. The same applies to other components of the spray ¬ wire. This results in the following conditions for the spray wire to be used according to the method: 21 - 0.8 * CrÄ>NiÄ> CrÄ - 8.
Im Folgenden wird ein Ausführungsbeispiel der Erfindung anhand einer Zeichnung näher erläutert. In the following an embodiment of the invention will be explained in more detail with reference to a drawing.
Dabei zeigt: Showing:
Fig. 1 das Schäffler-Diagramm mit den Rahmenbedingungen für die Legierungszusammensetzung einer geeigneten Funktionsschicht .  1 shows the Schäffler diagram with the framework conditions for the alloy composition of a suitable functional layer.
Gemäß diesem Ausführungsbeispiel wird die Funktionsschicht mittels Lichtbogendrahtspritzen (LDS) abgeschieden. Beim Lichtbogendrahtspritzen werden einem Beschichtungskopf zwei drahtförmige Spritzwerkstoffe zugeführt. Zwischen den According to this embodiment, the functional layer is deposited by means of arc wire spraying (LDS). In arc wire spraying, two wire-shaped spray materials are fed to a coating head. Between
drahtförmigen Spritzwerkstoffen wird ein Lichtbogen gezündet. Dabei schmilzt der drahtförmige Spritzwerkstoff und wird mittels eines Trägergases gezielt auf das zu beschichtende Substrat aufgebracht, wo er abkühlt, erstarrt und die wire-shaped spray materials, an arc is ignited. In this case, the wire-shaped spray material melts and is selectively applied by means of a carrier gas to the substrate to be coated, where it cools, solidifies and the
Funktionsschicht bildet. Functional layer forms.
Der drahtförmige Spritzwerkstoff umfasst im Wesentlichen eine Eisen-Chromlegierung. Der Spritzwerkstoff ist zumindest mit Kohlenstoff als Mikrolegierung derart gebildet, dass bereits beim Abkühlen des Spritzwerkstoffs weit überwiegend Martensit entsteht, nahezu kein Austenit und nur geringe Ferrit- Anteile . The wire-shaped spray material essentially comprises an iron-chromium alloy. The spray material is formed at least with carbon as a micro-alloy in such a way that predominantly martensite is formed during the cooling of the spray material, almost no austenite and only small amounts of ferrite.
In den Kenngrößen des Schäffler-Diamgramms ergibt sich für die Funktionsschicht folgende Zusammensetzung: In the parameters of the Schäffler diamgram, the following composition results for the functional layer:
CrÄ = 12,9 und NiÄ = 5,9  CrÄ = 12.9 and NiÄ = 5.9
Das Chromäquivalent ergibt sich dabei aus einem Chrom-Anteil von 12,3 Gew.-% und einem Silizium-Anteil von 0,38 Gew.-%. Das Nickeläquivalent ergibt sich dabei aus einem Nickel- Anteil von 0,3 Gew.-%, einem Kohlenstoff-Anteil von 0,18 Gew.-% und einem Mangan-Anteil von 0,4 Gew.-%. The chromium equivalent results from a chromium content of 12.3 wt .-% and a silicon content of 0.38 wt .-%. The nickel equivalent results from a nickel Proportion of 0.3 wt .-%, a carbon content of 0.18 wt .-% and a manganese content of 0.4 wt .-%.
Weitere Legierungsbestandteile dieser beispielhaften Other alloying components of this exemplary
Funktionsschicht sind Cu, AI und V mit jeweils knapp unter 0,1 Gew.-% sowie in geringeren Spuren P, W, Co, Mo und S. Functional layer are Cu, Al and V, each with just under 0.1 wt .-% and in minor lanes P, W, Co, Mo and S.
Der Hauptbestandteil der Legierung ist Eisen. The main component of the alloy is iron.
Die Mengenangaben sind in Gewichtsprozent jeweils bezogen auf ein Gesamtgewicht, falls keine anderen Angaben gemacht sind.  The quantities are in percent by weight in each case based on a total weight, unless otherwise specified.
Die erfindungsgemäße Funktionsschicht zeichnet sich besonders durch eine hohe Härte und Beständigkeit gegenüber Diesel- Kraftstoff mit einem hohen Schwefelanteil von 500 bis zu 1000 ppm aus, während Funktionsschichten nach dem Stand der The functional layer according to the invention is characterized in particular by a high hardness and resistance to diesel fuel with a high sulfur content of 500 to 1000 ppm, while functional layers according to the prior art
Technik bei Kontakt mit solchem Kraftstoff schneller Technology on contact with such fuel faster
verschleißen und korrodieren. wear out and corrode.
Erfindungsgemäß erfolgt das Beschichten des Substrats in dem der drahtförmige Spritzwerkstoff in einem Lichtbogen According to the invention, the coating of the substrate takes place in which the wire-shaped spray material in an arc
aufgeschmolzen und als eine Funktionsschicht auf dem Substrat abgeschieden wird. Das Aufschmelzen des drahtförmigen is melted and deposited as a functional layer on the substrate. The melting of the wire-shaped
Spritzwerkstoffs in dem Lichtbogen erfolgt bevorzugt bei einer Schmelzleistung von zumindest 9000 W, insbesondere mit einer Stromstärke von zumindest 250 A und/oder einer Spannung von zumindest 36 V. Dadurch können beim Aufschmelzen sehr feine Partikel erzeugt werden, welche wiederum die Bildung sehr dichter Schichtgefüge ermöglichen. Spray material in the arc is preferably carried out at a melting capacity of at least 9000 W, in particular with a current of at least 250 A and / or a voltage of at least 36 V. As a result, very fine particles can be generated during melting, which in turn allow the formation of very dense layer structure ,
Um die Absaugung der sehr feinen Partikel durch die To the suction of the very fine particles by the
Anlagenabsaugung möglichst gering zu halten, ist es It is to keep plant extraction as low as possible
vorteilhaft, den Partikelstrahl schnell auszugestalten (hohe Fluggeschwindigkeit) . Dies kann durch Verwendung einer Lavaldüse erfolgen, die z.B. in der DE 102008004607 AI beschrieben ist. advantageous to design the particle beam quickly (high airspeed). This can be done by using a Laval nozzle done, which is described for example in DE 102008004607 AI.
Der drahtförmiger Spritzwerkstoff 4 wird vorteilhaft mit einer Geschwindigkeit von maximal 12 m/s gefördert wird und der Strahl aufgeschmolzener Partikel mit einer The wire-shaped spray material 4 is advantageously conveyed at a maximum speed of 12 m / s and the jet of molten particles with a
Geschwindigkeit von maximal 20 m/s abgesaugt wird. Diese Parametergrenzen gewährleisten die Ausbildung bevorzugter Schichtgefüge ohne dass wesentliche Legierungsbestandteile abgesaugt werden oder Abdampfen. Speed of a maximum of 20 m / s is sucked. These parameter limits ensure the formation of preferred layered structures without the extraction of essential alloy constituents or evaporation.
Außerdem ist es vorteilhaft Druckeigenspannungen der It is also advantageous residual compressive stresses of
Funktionsschicht durch Temperieren im Heizofen oder durch lokales induktives Erwärmen zu erzeugen, da diese die Haftung der Funktionsschicht am Substrat verbessern. Functional layer to produce by tempering in the heater or by local inductive heating, since these improve the adhesion of the functional layer to the substrate.

Claims

Patentansprüche claims
Reibleistungsreduzierte FunktionsSchicht, Friction-reduced functional layer,
umfassend eine Eisenbasislegierung comprising an iron-based alloy
mit überwiegend martensitischem Gefüge, with predominantly martensitic structure,
aufweisend folgende Legierungsbestandteile angegeben in den Kenngrößen Nickeläquivalent (NiÄ) und Chromäquivalent (CrÄ) des Schäffler-Diagramms : comprising the following alloy constituents indicated in the parameters nickel equivalent (NiÄ) and chromium equivalent (CrÄ) of the Schäffler diagram:
- CrÄ > 10 und  - CrÄ> 10 and
- NiÄ > CrÄ - 9 und  - NiÄ> CrÄ - 9 and
- NiÄ < 19 - 0,8*CrÄ  - NiA <19 - 0.8 * CrÄ
jeweils bezogen auf ein Gesamtgewicht. each based on a total weight.
Funktionsschicht nach Anspruch 1, Functional layer according to claim 1,
dadurch gekennzeichnet, dass characterized in that
- Mangan mit einem Anteil von 0,3 Gew.% bis 2 Gew.%, vorzugsweise von 0,3 bis 0,8 Gew.%, und/oder  Manganese in a proportion of 0.3% by weight to 2% by weight, preferably from 0.3 to 0.8% by weight, and / or
- Silizium mit einem Anteil von 0,01 Gew.% bis 1 Gew.%, vorzugsweise von 0,2 bis 0,6 Gew.-%, und/oder  - Silicon in a proportion of 0.01 wt.% To 1 wt.%, Preferably from 0.2 to 0.6 wt .-%, and / or
- Molybdän mit einem Anteil von 0,01 Gew.% bis 1 Gew.%, vorzugsweise von 0,2 bis 0,6 Gew.-%, und/oder  Molybdenum in a proportion of 0.01% by weight to 1% by weight, preferably from 0.2 to 0.6% by weight, and / or
- Niob mit einem Anteil von 0,01 Gew.% bis 1 Gew.%, vorzugsweise von 0,2 bis 0,6 Gew.-%,  Niobium in an amount of from 0.01% by weight to 1% by weight, preferably from 0.2 to 0.6% by weight,
wobei die Summe aus Niob- und Nickel-Anteil < 1 Gew.-% und/oder wherein the sum of niobium and nickel content <1 wt .-% and / or
- Titan mit einem Anteil von 0,001 Gew.% bis 0,02 Gew.%, vorzugsweise von 0,005 bis 0,01 Gew.-%,  Titanium at a level of from 0.001% by weight to 0.02% by weight, preferably from 0.005 to 0.01% by weight,
jeweils bezogen auf ein Gesamtgewicht, enthalten sind. Verfahren zum Beschichten eines Substrats, each based on a total weight included. Method for coating a substrate,
bei dem ein drahtförmiger Spritzwerkstoff in einem in which a wire-shaped spray material in one
Lichtbogen aufgeschmolzen und als eine Funktionsschicht auf dem Substrat abgeschieden wird, dadurch  Arc is melted and deposited as a functional layer on the substrate, characterized
gekennzeichnet, in
dass ein Spritzdraht auf Eisenbasis verwendet wird, aufweisend folgende Legierungsbestandteile angegeben in den Kenngrößen Nickeläquivalent (NiÄ) und Chromäquivalent (CrÄ) des Schaffler-Diagramms : in that an iron-based spray wire is used, comprising the following alloy constituents indicated in the parameters nickel equivalent (NiAe) and chromium equivalent (CrA) of the Schaffler diagram:
- CrÄ > 10,5 und  - CrÄ> 10.5 and
- NiÄ > CrÄ - 8 und  - NiÄ> CrÄ - 8 and
- NiÄ < 21 - 0, 8*CrÄ  - NiA <21 - 0, 8 * CrÄ
jeweils bezogen auf ein Gesamtgewicht. each based on a total weight.
Verfahren nach Anspruch 3, Method according to claim 3,
dadurch gekennzeichnet, characterized,
dass der drahtförmige Spritzwerkstoff that the wire-shaped spray material
zusätzliche folgende Legierungsbestandteile umfasst: additional alloying components include:
Mangan mit einem Anteil von 0,3 Gew.% bis 2 Gew.%, vorzugsweise von 0,3 bis 0,8 Gew.%, und/oder  Manganese in a proportion of 0.3 wt.% To 2 wt.%, Preferably from 0.3 to 0.8 wt.%, And / or
- Silizium mit einem Anteil von 0,01 Gew.% bis 1 Gew.%, vorzugsweise von 0,2 bis 0,6 Gew.-%, und/oder  - Silicon in a proportion of 0.01 wt.% To 1 wt.%, Preferably from 0.2 to 0.6 wt .-%, and / or
- Molybdän mit einem Anteil von 0,01 Gew.% bis 1 Gew.%, vorzugsweise von 0,2 bis 0,6 Gew.-%, und/oder  Molybdenum in a proportion of 0.01% by weight to 1% by weight, preferably from 0.2 to 0.6% by weight, and / or
- Niob mit einem Anteil von 0,01 Gew.% bis 1 Gew.%, vorzugsweise von 0,2 bis 0,6 Gew.-%,  Niobium in an amount of from 0.01% by weight to 1% by weight, preferably from 0.2 to 0.6% by weight,
wobei die Summe aus Niob- und Nickel-Anteil < 1 Gew.-% und/oder wherein the sum of niobium and nickel content <1 wt .-% and / or
- Titan mit einem Anteil von 0,001 Gew.% bis 0,02 Gew.%, vorzugsweise von 0,005 bis 0,01 Gew.-%,  Titanium at a level of from 0.001% by weight to 0.02% by weight, preferably from 0.005 to 0.01% by weight,
jeweils bezogen auf ein Gesamtgewicht. each based on a total weight.
PCT/EP2013/001574 2012-06-29 2013-05-28 Method for coating a substrate with a spray material and functional layer achievable with this method WO2014000849A2 (en)

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DE102010021300A1 (en) 2010-05-22 2011-11-24 Daimler Ag Wire-shaped spray material, functional layer that can be produced therewith and method for coating a substrate with a spray material

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DE102012013020B3 (en) 2013-05-02
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CN104603318A (en) 2015-05-06
US20150152539A1 (en) 2015-06-04
JP6053230B2 (en) 2016-12-27
EP2867383A2 (en) 2015-05-06
WO2014000849A3 (en) 2014-03-27

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